The present invention relates to new and improved thermoelectric devices for the generation of electricity.
It has been recognized that the world supply of fossil fuels for the production of energy is being exhausted at ever increasing rates. This realization has resulted in an energy crisis which impacts not only the world's economy, but threatens the peace and stability of the world. The solution to the energy crisis lies in the development of new fuels and more efficient techniques to utilize them. To that end, the present invention deals with energy conservation, power generation, pollution, and the generation of new business opportunities by the development of new thermoelectric devices which provide more electricity.
An important part of the solution with respect to the development of permanent, economical energy conversion lies in the field of thermoelectrics wherein electrical power is generated by heat. It has been estimated that more than two-thirds of all our energy, for example, from automobile exhausts or power plants, is wasted and given off to the environment. Up until now, there has been no serious climatic effect from this thermal pollution. However, it has been predicted that as the world's energy consumption increases, the effects of thermal pollution will ultimately lead to a partial melting of polar ice caps with an attendant increase in sea level.
The efficiency of a thermoelectric device can be expressed in terms of a figure of merit (Z) for the material forming the device, the equation defining Z is: EQU Z=(S.sup.2.sigma. /K
where:
Z is expressed in units.times.10.sup.3 ; PA1 S is the Seebeck coefficient in .mu.V/.degree.C; PA1 K is the thermal conductivity in mW/cm-.degree.C; and PA1 .sigma.is the electrical conductivity in (.OMEGA.-cm).sup.-1
From the above, one can see that in order for a material to be suitable for thermoelectric power conversion, it must have a large value for the thermoelectric power Seebeck coefficient (S), a high electrical conductivity (.sigma.), and a low thermal conductivity (K). Further, there are two components to the thermal conductivity (K): K.sub.1, the lattic component; and K.sub.e, the electrical component. In non-metals, K.sub.1 dominates and it is this component which mainly determines the value of K.
Stated in another way, in order for a material to be efficient for thermoelectric power conversion, it is important to allow carriers to diffuse easily from the hot junction to the cold junction while maintaining the temperature gradient. Hence, high electrical conductivity is required along with low thermal conductivity.
Thermoelectric power conversion has not found wide usage in the past. The major reason for this is that prior art thermoelectric materials which are at all suitable for commercial applications have been crystalline in structure. Crystalline solids cannot attain large values of electrical conductivity while maintaining low thermal conductivity. Most importantly, because of crystalline symmetry, thermal conductivity cannot be controlled by modification.
In the case of the conventional polycrystalline approach, the problems of single crystalline materials still dominate. However, new problems are also encountered by virtue of the polycrystalline grain boundaries which cause these materials to have relatively low electrical conductivities. In addition, the fabrication of these materials is also difficult to control as a result of their more complex crystalline structure. The chemical modification or doping of these materials, because of the above problems are especially difficult.
Among the best known currently existing polycrystalline thermoelectric materials are (Bi,Sb).sub.2 Te.sub.3, PbTe, and Si-Ge. The (Bi,Sb).sub.2 Te.sub.3 materials are best suited for applications in the -10.degree. C. to 150.degree. C. range with its best Z appearing at around 30.degree. C. (Bi,Sb).sub.2 Te.sub.3 represents a continuous solid solution system in which the relative amount of Bi and Sb are from 0 to 100%. The Si-Ge material is best suited for high temperature applications in the 600.degree. C. to 1000.degree. C. range with a satisfactory Z appearing at above 700.degree. C. The PbTe polycrystalline material exhibits its best figure of merit in the 300.degree. C. to 500.degree. C. range. None of these materials is well suited for applications in the 100.degree. C. to 300.degree. C. range. This is indeed unfortunate, because it is in this temperature range where a wide variety of waste heat applications are found. Among such applications are geothermal waste heat and waste heat from internal combustion engines in, for example, trucks, buses, and automobiles. Applications of this kind are important because the heat is truly waste heat. Heat in the higher temperature ranges must be intentionally generated with other fuels and therefore is not truly waste heat.
New and improved thermoelectric alloy materials have been discovered for use in the aforesaid temperature ranges. These materials are disclosed and claimed in copending U.S. application Ser. No. 412,306, filed August 27, 1982, now U.S. Pat. No. 4,447,277, in the names of Tumkur S. Jayadev and On Van Nguyen for NEW MUTLIPHASE THEREMOELECTRIC ALLOYS AND METHOD OF MAKING SAME, allowed Sept. 26, 1983, and U.S. application Ser. No. 414,917, filed Sept. 3, 1982 in the names of Tumkur S. Jayadev, On Van Nguyen, Jamie M. Reyes, Helen Davis and Michael W. Putty for NEW POWDER PRESSED THERMOELECTRIC MATERIALS AND METHOD OF MAKING SAME.
The thermoelectric materials there disclosed can be utilized in the device herein. These materials are not single phase crystalline materials, but instead, are disordered materials. Further, these materials are multiphase materials having both amorphous and multiple crystalline phases. Materials of this type are good thermal insulators. They include grain boundaries of various transitional phases varying in composition from the composition of matrix crystallites to the composition of the various phases in the grain boundary regions. The grain boundaries are highly disordered with the transitional phases including phases of high thermal resistivity to provide high resistance to thermal conduction. Contrary to conventional materials, the material is designed such that the grain boundaries define regions including conductive phases therein providing numerous electrical conduction paths through the bulk material for increasing electrical conductivity without substantially effecting the thermal conductivity. In essence, these materials have all of the advantages of polycrystalline materials in desirably low thermal conductivities and crystalline bulk Seebeck properties. However, unlike the conventional polycrystalline materials, these disordered multiphase materials also have desirably high electrical conductivities. Hence, as disclosed in the aforesaid referenced applications, the S.sup.2 .sigma. product for the figure of merit of these materials can be independently maximized with desirably low thermal conductivities for thermoelectric power generation.
Amorphous materials, representing the highest degree of disorder, have been made for thermoelectric applications. The materials and methods for making the same are fully disclosed and claimed, for example, in U.S. Pat. Nos. 4,177,473, 4,177,474, and 4,178,415 which issued in the name of Stanford R. Ovshinsky. The materials disclosed in these patents are formed in a solid amorphous host matrix having structural configurations which have local rather than long-range order and electronic configurations which have an energy gap and an electrical activation energy. Added to the amorphous host matrix is a modifier material having orbitals which interact with the amorphous host matrix as well as themselves to form electronic states in the energy gap. This interaction substantially modifies the electronic configurations of the amorphous host matrix to substantially reduce the activation energy and hence, increase substantially the electrical conductivity of the material. The resulting electrical conductivity can be controlled by the amount of modifier material added to the host matrix. The amorphous host matrix is normally of intrinsic-like conduction and the modified material changes the same to extrinsic-like conduction.
As also disclosed therein, the amorphous host matrix can have lone-pairs having orbitals wherein the orbitals of the modifier material interact therewith to form the new electronic states in the energy gap. In another form, the host matrix can have primarily tetrahedral bonding wherein the modifier material is added primarily in a non-substitutional manner with its orbitals interacting with the host matrix. Both d and f band materials as well as boron and carbon, which add multiorbital possibilities can be used as modifiers to form the new electronic states in the energy gap.
As a result of the foregoing, these amorphous thermoelectric materials have substantially increased electrical conductivity. However, because they remain amorphous after modification, they retain their low thermal conductivities making them well suited for thermoelectric applications, especially in high temperature ranges above 400.degree. C.
These materials are modified on an atomic or microscopic level with the atomic configurations thereof substantially changed to provide the heretofore mentioned independently increased electrical conductivities. In contrast, the materials disclosed in the aforesaid referenced applications are not atomically modified. Rather, they are fabricated in a manner which introduces disorder into the material on a macroscopic level. This disorder allows various phases including conductive phases to be introduced into the material much in the same manner as modification atomically in pure amorphous phase materials to provide controlled high electrical conductivity while the disorder in the other phases provides low thermal conductivity. These materials therefore are intermediate in terms of their thermal conductivity between amorphous and regular polycrystalline materials.
A thermoelectric device generates electricity by the establishment of a temperature differential across the materials contained therein. The thermoelectric devices generally include elements of both p-type and n-type material. In the p-type material the temperature differential drives positively charged carriers from the hot side to the cold side of the elements, while in the n-type material the temperature differential drives negatively charged carriers from the hot side to the cold side of the elements.
Thermoelectric power conversion has not found wide usage in the past not only because of material limitations but also because of device limitations. Among the device limitations are bowing or warping of device substrates, loss of broad surface contact between the device and a heat exchanger when utilized in a thermoelectric system and temperature losses across the substrates.
Thermoelectric devices of the prior art use copper lead patterns placed upon a ceramic substrate for the attachment of thermoelectric elements thereto. In the manufacture of these devices, a second ceramic substrate having another copper lead pattern is sweated onto the thermoelectric elements. Due to the difference in the coefficient of thermal expansion between the ceramic substrates and the copper lead patterns, there occurs a bowing or warping of the substrates during the sweating operation which causes a number of related problems.
First, because of the warping of the substrates, it is difficult if not impossible to obtain a good thermal connection between the elements and the copper lead patterns of the substrates. Additionally, because the ceramic substrates are brittle, the bowing or warping, if severe enough, can cause cracking of the substrates and other physical degradation of the devices. Furthermore, to be employed in a thermoelectric system, the outer surfaces of the substrates must make intimate broad surface contact with a heat exchanger. The warping or bowing of the substrates also makes proper connection between the devices and a heat exchanger difficult.
To overcome these problems, the forces imparted to the substrates caused by the difference in the coefficients of thermal expansion between the copper lead patterns and the ceramic substrates are equalized by applying copper in substantially identical patterns as the lead patterns to the other side of the substrates. Unfortunately, the additional copper increases the material cost of the devices and adds extra processing steps to their manufacture. Furthermore, the degree of abatement of thermal stress obtained by this process is still not satisfactory.
During the operation of thermoelectric devices, a temperature differential is applied across the device to generate electricity. Due to the difference in the coefficient of thermal expansion between the substrates and the thermoelectric elements, loss of broad surface contact occurs between the device and the heat exchanger when utilized in a thermoelectric system. This loss of broad surface contact results in less heat transfer which translates to a lower temperature differential across the device, and lower efficiency of the device.
It has also been found that a substantial temperature drop occurs across the ceramic substrates. The voltage output and the current of a thermoelectric element is proportional to the temperature differential across the element. Therefore, the power is proportional to the square of the temperature differential, and any change in temperature differential across the elements has a substantial effect on the power output of the device. As a result, the temperature drop across the substrates reduces the temperature differential otherwise available to the elements for power generation. Further, the additional copper used to overcome the warping problems adds additional temperature losses across the substrates. These losses undesirably decrease the temperature differential across the thermoelectric elements from the temperature differential available across the devices thereby adversely decreasing the power output of the devices.
Because of these problems, thermoelectric devices of the prior art often failed during operation due to cracking of thermoelectric elements, loosening of electrical and thermal connections and fracture of the substrate. Furthermore, warpage and loss of broad surface contact results in lower heat transfer which translates into a lower temperature differential across the device and therefore, a lower overall efficiency.
In an attempt to overcome these problems, a substrateless device has been proposed. This device and method of fabrication thereof is disclosed and claimed in co-pending U.S. application Ser. No. 372,688, filed Apr. 28, 1982, in the name of Der-Jeou Chou for IMPROVED THERMOELECTRIC DEVICE AND METHOD OF MAKING SAME, allowed Mar. 7, 1984, which application is also incorporated herein by reference. The device disclosed therein has no substrates and no compensating elements. Consequently, thermal losses normally resulting from these components are eliminated. Furthermore, the disclosed device exhibits a lower degree of thermal stress because the thermoelectric generating elements are flexibly held together by a plurality of conductive interconnecting members and a potting compound filling the voids between the elements. This structure results in a device having a high degree of flexibility.
Two other important considerations which are often problematical in working with thermoelectric devices are the exact dimensions and configuration of thermal elements within a particular device. These are determined by a number of detailed design considerations. Not the least among these are the required poweroutput as well as the overall device dimensions. Some of the factors involved in these two considerations are discussed in, for example, Raag, U.S. Pat. No. 4,032,363, and Germano, U.S. Re-issue Pat. No. 30,652. In his discussion of some of the factors effecting these considerations, Raag notes that many thermoelectric materials do not have the mechanical strength required to allow them to be fashioned into thermoelectric elements with the extreme length to cross sectional element area ratio required of devices producing high voltages. Therefore, a situation is often presented wherein the only truly feasible way to manufacture a thermoelectric device thin enough for the physical limitations of a particular application is to make the electrical connections between individual thermoelectric elements as thin as possible. However as noted in Germano, supra, it is important that the connections between the individual thermoelectric elements be of negligible electrical resistance in relation to the elements themselves. Furthermore, bearing in mind the basic electrical relation R=.rho.1/A, it is obvious that one cannot merely make the connections thinner without adversely affecting, i.e. increasing, the resistance of the connection. Indeed, Raag, in the course of his discussion of one alternative method for electrical interconnection of the thermoelectric elements in a thermoelectric device, says at the bottom of column 16 and top of column 17, "The electrical resistivity of the metal should be quite low, but any deficiency in this regard can be effectively eliminated by the use of thicker metal layers." Obviously, while this deals quite effectively with the problem of the resistivity of the connections between the elements, it is clearly counter productive in terms of minimizing overall device size.
The second consideration noted above, the power output of the device, is also discussed in Raag. He notes that the power output of a device generally decreases with an increasing ratio of individual thermoelectric element length to cross sectional area. However, by increasing the individual thermoelectric element length to cross sectional area ratio a substantially thinner device can be achieved. So, in the use of prior art thermoelectric devices, there is often a direct conflict between the design considerations in making a thinner device versus the considerations required for a given power output and device efficiency.
As will be demonstrated hereinafter, the new and improved thermoelectric devices of the instant invention overcome the problems of the prior art. A thinner device is achieved while increasing power output substantially.